Thermosettable compositions and thermosets therefrom

Abstract

A thermosettable (curable) epoxy resin composition including (A) a residual oligomeric product; wherein the residual oligomeric product comprises a polyfunctional aliphatic or cycloaliphatic epoxy resin which has been isolated from an epoxy resin product formed as a result of an epoxidation process comprising the reaction of (i) an aliphatic or cycloaliphatic hydroxyl-containing material with (ii) an epihalohydrin, (iii) a basic-acting substance, (iv) a non-Lewis acid catalyst, and (V) optionally one or more solvents; (B) an epoxy curing material comprising (i) an epoxy resin curing agent, (ii) an epoxy resin catalyst, or both an epoxy resin curing agent (i) and an epoxy resin catalyst (ii); and (C) optionally, an epoxy resin compound other than the aliphatic or cycloaliphatic polyfunctional epoxy resin (A). A thermoset may also be made from the above thermosettable composition.

What is claimed is: 
     
       1. A thermosettable epoxy resin composition comprising
 (A) a residual oligomeric product; wherein the residual oligomeric product comprises a polyfunctional aliphatic or cycloaliphatic epoxy resin which has been isolated from an epoxy resin product formed as a result of an epoxidation process comprising the reaction of
 (i) an aliphatic or cycloaliphatic hydroxyl-containing material; 
 (ii) an epihalohydrin; 
 (iii) a basic-acting substance; 
 (iv) a non-Lewis acid catalyst; and 
 (v) optionally, one or more solvents; 
 
 (B) an epoxy curing material comprising
 (i) an epoxy resin curing agent; 
 (ii) an epoxy resin curing catalyst; or 
 (iii) both (i) and (ii); and 
 
 (C) optionally, an epoxy resin compound other than the polyfunctional aliphatic or cycloaliphatic epoxy resin (A). 
 
     
     
       2. The composition of  claim 1  wherein the aliphatic or cycloaliphatic hydroxyl containing material is selected from the group consisting of cyclohexanedialkanols; cyclohexenedialkanols; cyclohexanolmonoalkanols; cyclohexenolmonoalkanols; decahydronaphthalenedialkanols; octahydronaphthalenedialkanols; 1,2,3,4-tetrahydronaphthalenedialkanols; and bridged cyclohexanols. 
     
     
       3. The composition of  claim 2  wherein the aliphatic or cycloaliphatic hydroxyl containing material is selected from the group consisting of cyclohexanedialkanols and cyclohexenedialkanols. 
     
     
       4. The composition of  claim 2  wherein the aliphatic or cycloaliphatic hydroxyl containing material is selected from the group consisting of cis-, trans-1,3- and 1,4-cyclohexanedimethanol; cis-, trans-1,2-cyclohexanedimethanol; cis-, trans-1,3-cyclohexanedimethanol; cis-, trans-1,4-cyclohexanedimethanol; a methyl substituted cyclohexanedimethanol; 1,1-cyclohexanedimethanol; a cyclohexenedimethanol; 3-cyclohexene-1,1-dimethanol, 6-methyl-; 4,6-dimethyl-3-cyclohexene-1,1-dimethanol; cyclohex-2-ene-1,1-dimethanol; 1,1-cyclohexanediethanol; 1,4-bis(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexanediethanol; 1,4-(2-hydroxyethyloxy)cyclohexane; and 1,4-(2-hydroxyethyloxy)cyclohex-2-ene. 
     
     
       5. The composition of  claim 1  wherein the cycloaliphatic hydroxyl containing material comprises a material selected from the group consisting of cycloaliphatic diols, polycycloaliphatic diols, monol monoalkanols and dialkanols. 
     
     
       6. The composition of  claim 1  wherein the aliphatic hydroxyl containing material comprises a material selected from the group consisting of alkoxylated phenolic reactants; alkoxylation products of the hydrogenated aromatic phenolic reactants; neopentyl glycol; trimethylol propane; ethylene glycol; propylene glycol; triethylene glycol; higher alkoxylated ethylene glycols; pentaerythritol; 1,4-butanediol; 1,6-hexanediol; 1,12-dodecandiol; and mixtures thereof. 
     
     
       7. The composition of  claim 1  wherein the polyfunctional aliphatic or cycloaliphatic epoxy resin of the residual oligomeric product has been isolated from diglycidyl ethers of cis-, trans-1,3- and 1,4-cyclohexanedimethanols; wherein the polyfunctional aliphatic or cycloaliphatic epoxy resin of the residual oligomeric product contains less than 20% by weight of diglycidyl ethers of cis-, trans-1,3- and 1,4-cyclohexanedimethanols and comprises one or more selected from the group consisting of:
 geometrical isomers of 2-propanol, 1-(oxiranylmethoxy)-3-[[3(or 4)-[(oxiranylmethoxy) methyl]cyclohexyl]methoxyl]-; 
 geometrical isomers of oxirane, 2-[[2-chloro-1-[[[3(or 4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]-; 
 geometrical isomers of oxirane, 2-[[[3(or 4)-[[2,3-bis(oxiranylmethoxy)propoxy]methyl]cyclohexyl]methoxy]methyl]-; 
 geometrical isomers of cyclohexanemethanol, 3(or 4)-[[2-hydroxy-3-[[3(or 4)-[(oxiranyl-methoxy)methyl]cyclohexyl]methoxy]propoxy]methyl]-; 
 geometrical isomers of 2-propanol, 1,3-bis[[3(or 4)-[(oxiranylmethoxy)methyl] cyclohexyl]methoxy]-; and 
 geometrical isomers of oxirane, 2-[[2-[[3(or 4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]-1-[[[3(or 4)-[(oxiranylmethoxy)methyl]cyclohexyl]methoxy]methyl]ethoxy]methyl]-. 
 
     
     
       8. The composition of  claim 1 , wherein the curing material (B) comprises one or more alkyleneamine or polyalkylenepolyamine curing agents. 
     
     
       9. The composition of  claim 1 , including (C) one or more epoxy resins other than the epoxy resin of component (A). 
     
     
       10. The composition of  claim 9 , wherein the one or more epoxy resins, component (C), comprises one or more of aliphatic and/or cycloaliphatic epoxy resins. 
     
     
       11. A partially cured (B-staged) product comprising the partially cured thermosettable epoxy resin composition of  claim 1 . 
     
     
       12. A totally cured thermoset product comprising the totally cured thermosettable epoxy resin composition of  claim 1 . 
     
     
       13. An article made from the composition of  claim 1 . 
     
     
       14. The article of  claim 13 , wherein the article comprises a coating, a laminate, an encapsulation, a casting, a filament winding, a molding, a polymer concrete, an adhesive bond, a paint, a lacquer, a varnish, or a composite. 
     
     
       15. A process for preparing a thermosettable composition comprising admixing:
 (A) a residual oligomeric product; wherein the residual oligomeric product comprises a polyfunctional aliphatic or cycloaliphatic epoxy resin which has been isolated from an epoxy resin product formed as a result of an epoxidation process comprising the reaction of
 (i) an aliphatic or cycloaliphatic hydroxyl-containing material; 
 (ii) an epihalohydrin; 
 (iii) a basic-acting substance; 
 (iv) a non-Lewis acid catalyst; and 
 (v) optionally, one or more solvents; 
 
 (B) an epoxy curing material comprising
 (i) an epoxy resin curing agent; 
 (ii) an epoxy resin curing catalyst; or 
 (iii) both (i) and (ii); and 
 
 (C) optionally, an epoxy resin compound other than the polyfunctional aliphatic or cycloaliphatic epoxy resin (A). 
 
     
     
       16. A process of curing an admixture composition comprising: preparing a thermosettable composition according to the method of  claim 15 , and curing the thermosettable composition at a temperature of from about 0° C. to about 300° C.